United States Patent [191

Aczel et al.

[11] [45]
Assistant Examiner—J. Thierstein

Apr. 18, 1978



LIQUEFACI‘ION PROCESS [75] Inventors: Thomas Aczel; Karl W. Plumlee, both of Baytown, Tex.

Attorney, Agent, or Firm—Llewellyn A. Proctor



[73] Assignee: Exxon Research & Engineering Co.,
Linden, NJ.

An indigenous aqueous stream can be treated and then recycled, with a suitable donor solvent, to a coal lique

[21] Appl. No: 755,174 [221

Dec. 29, 1976

faction zone to catalyze the reaction. In one embodi ment, an aqueous fraction is separated from a coal lique faction zone ef?uent, a quinone solids portion of the

separated fraction is concentrated within the liquid by
evaporation of water therefrom to form a slurry, and the slurry is then recycled to the coal liquefaction zone to catalyze the coal liquefaction reaction. Naturally

Related U.S. Application Data
Continuation-impart of Ser. No. 686,813, May 17,
1976, Pat. No. 4,049,536, and a continuation-in-part of

Ser. No. 686,814, May 17, 1976, Pat. No. 4,049,537, and a continuation-in-part of Ser. No. 686,827, May 17, 1976, Pat. No. 4,051,012, and a continuation-in-part of Ser. No. 686,828, May 17, 1976.

occurring phenols and alkyl substituted phenols, also
found within the aqueous stream, can also be converted

to quinones, if desired, by a chemical reaction which favors the addition of hydroxyl consitutents to the phe
nols to form dihydroxy benzenes. Quinones, as dis

[51] [52] [53] [56]

Int. Cl.2 ........................................... .. C10G 1/06 U.S. Cl. ............. .. 208/10; 208/8
Field of Search ...... . . . . . . . . . . .. 208/8, 10

closed in copending Applications Ser. No. 686,813 now
U.S. Pat. No. 4,049,536; Ser. No. 686,814 now U.S. Pat. No. 4,049,537; Ser. No. 686,827 now U.S. Pat. No. 4,051,012 and Ser. No. 686,828, K. W. Plumlec et al,

References Cited

3,700,583 10/1972 Salamony et al. ..................... .. 208/8

?led May 17, 1976, are suitable hydrogen transfer cata


Primary Examiner-Delbert E, Gantz

7 Claims, 1 Drawing Figure


. _






Q mxER











aso—|ooo° F




fraction) is rehydrogenated in a hydrotreater. and the fragments may remain with. and the hydrogenated F.S.-400° F. and treatment because. 686. the donor solvent interest among known coal conversion processes for the fraction is hydrotreated in a hydrogenation zone in the production of useful petroleum-like liquids. which . Pat. the quinones accelerate the transfer of process. hydrocar lizes a rich mixture of the ortho. 686. such process has nonetheless been found susceptible of further im provement. or both. In such processes. The Salamony et a1 process describes the trated by evaporation of liquid from the aqueous phase use of quinones.S. if sufficiently small may be evolved as a portion of the desired pe troleum-like liquid product.+ bottoms. admixed and slurried with fresh coal. donor. In the Plumlee et al pro cess a particulate coal feed is admixed with a hydrogen donor solvent to which a quinone has been added. offers these and other advantages over prior art processes.827 now U. reactive free radicals. also contains phe amount of liquid products.814 now U. Pat.. e..e. and in the breaking coal molecules each bond rupture results in the formation of extremely to the more effective hydrogen transfer produced by the quinone catalyst which suppresses recombination of the free radicals that tend to form high boiling poly mers. Pat. 4. liquids and solids are inevitably formed. as disclosed. there being suit uct.051. in any 35 quinone catalysts are recovered.. fraction is comprised of hydrogen donor compounds and accordingly. Nos. If the moities become ex Whereas the process of Plumlee et al. admixed or slurried with fresh coal. when early stabi lized by the addition of a hydrogen atom. and 1000" F.S. or form a part of the char or coke that is Among the objects of this invention are: To provide a new and improved process wherein produced.— petroleum-like liquid products.S. No. often a liquid fraction derived from within the Salamony et al. particularly quinone derivatives of 55 to form a thick slurry and then recycled without further mono. quinone compounds.and/or polynuclear aromatic compounds.S.814 now U. ~ liquid products. The 45 with the present invention wherein it has been discov ered that an indigenous aqueous stream can be treated and the hydrocarbonaceous effluent slurry is fraction ated into C. this resulting in an in cracked and cleaved from the disintegrating coal solids. the latter being discarded as a waste stream.827 now U.813 now U. as molecules are thermally hydrogen to stabilize the free radicals formed by the disintegrating coal molecules. i.e. In accordance with a further embodiment. 1976.012 catalysts in coal liquefaction processes as disclosed in U.049. ?led May 686.g. No. I cessively large before they are stabilized. and effectively utilized to avoid repolymerization of the moities to form char or coke.537. indigenous 700°-1000° F. of these reactions.828 by Plumlee et al. hydroquinone compounds. the quinone solids are merely concen Oct. In the various competing reactions. 686. with decreased amounts of char to concentrate indigenous quinone solids (i. Pat.049. 3.583 issued to Salamony et al on ferred aspects. 24.012. or admixture thereof) within the aqueous phase to form a slurry. unlike the process of solvent. or hydrotreating zone (or zones). and the mixture is then reacted in a coal liquefaction zone at Hydrogen donor solvent processes for use in the 10 conditions suf?cient to hydroconvert and liquefy the coal. catalyze either. and and then recycled to the coal liquefaction zone. in accordance with Salamony et a1.536.S. the separated frac¥ vert indigenous phenolic components of the aqueous fraction into catalytic quinone components. as measured by an increase 60 nols. Typically the C1-400" F. undesirable 1000“ F. No.828. if desired. however. 686. the quinones are present certain halogens and hydrogen halides as carbon-radical as the major component of the solids and are catalyti scavengers which are added with the hydrogen donor cally active without further treatment.051. No. Pat. crushed coal is solvent fraction is then recycled to said coal liquefac contacted at elevated temperature and pressure with a tion zone. To provide a new and improved hydrogen donor coal liquefaction process. in total amount of benzene-soluble liquids in the prod also be converted to hydroquinones. 1972.S. These moities. fraction of the liquid product radical scavengers. 400°-750° F. Pat.1 HYDROGEN DONOR SOLVENT COAL 4. all or a portion of this fraction (or a 400°-850° F.+ liquid products can form. 50 the slurry then recycled to the coal liquefaction zone Quinones have been employed as carbon radical scav (or zones).dihydroxy event. gases. which acts as a hydrogen transfer agent or and 686. A preferred technique for adding quinones to the able quinone catalysts for effecting hydrogen transfer solvent.and para. and 686. No.S.hydrogen transfer LIQUEFACI‘ION PROCESS RELATED APPLICATION This is a continuation-in-part of Application Ser. the moities can form polymeric products. however. 4. to engers in coal liquefaction processes. supra. 4. Also.536. These objects and others are achieved in accordance phase. No. 4. the solids containing slurry is separated from tion is contacted with a peroxygen compound to con in an oxidation zone to form the quinones. in situ. crease in liquid yield and decrease of coke or char due Coal is largely comprised of polymerized multi-ring aromatic structures. In conventional practice. ?led May 17. application Ser.032 2 Quinones have also been used as.. or both. 750°-1000° F.813 now U. or regenerated in situ within a hydrogen donor solvent process. Nos. albeit efforts continue to increase the amount of petroleum-like liq uids that are formed. and alkyl substituted phenols which can. The solids por solvent fed to the coal liquefaction zone to increase the tion of the aqueous stream. and then to recycle such stream via the coal mixing zone to the coal liquefaction zone. Sufficient hydrogen must be available. 1976. the gases are separated from the heavier products 40 benzene isomers produced in situ and employed as a catalyst to produce greater quantities of the more useful petroleum-like liquids.085. or carbon 65 the coal liquefaction zone effluent. The solvent supplies hydrogen to the hydrogen de?cient coal molecules. generally. therefore. No. and coke. 4. 686. Pat. In its pre in U. The products are then separated into fractions hydrogenation and liquefaction of coal are of particular inclusive of a donor solvent fraction. and then recycled to the coal liquefaction zone to catalyze the coal liquefaction reac tion and produce desirable 1000° F. particularly one which uti bon fraction is separated from an indigenous aqueous 400°—750° F. 1000° presence of the quinone catalyst. is to treat an reactions. 4. In this process.537.

and from about 4 pounds to about 13 about 3 rings in the total molecule. sulfuric acid. and about 0. i. methyl. The peroxygen compound is added in amount suffi 40 In a preferred embodiment. major components are such species as ortho and para In one embodiment. or can contain both fused and non fused rings.085. but the diqui-. Clo-C1‘. or a reaction product of hydro 700° F. or hydroquinones. preferably from . a portion of the water is evapo rated from the aqueous liquid and the slurry is recycled 25 Polynuclearpolyquinones are present. preferably suitable as a solvent donor. The rings canbe substituted or unsub phase is found to contain a major concentration of qui none compounds suitable per se as hydrogen transfer stituted. the generated admixture of quinone compounds. a quinone compound of such admixture being identi?ed as a‘compound wherein two keto or hydroxy groups are connected by a system of conjugated double bonds. Pressure is not critical. and preferably from about 400' to about organic carboxylic acid... butanoic acid. and a lesser quantity of phenolic materials which can. the rings constituting the molecule can be about 25 pounds of the 400° F. but preferably 65 hexahydro?uorine. the hydro each are added in amounts ranging from about 0. gen peroxide and organic carboxylic acid can be added in substantially stoichiometric amounts. vWhere such amounts of hydrogen donor compounds are not present carboxylic acid. of quinone compounds. Preferred hydrogen donor compoundsare added to. a strong mineral acid is added to catalyze the hydroxylation reaction. and generally contain about 30 percent.6 moles.1 to about 2 percent. be converted into quinone com from 6 to about 20 carbon atoms. or an admixture of hydrogen peroxide and an 45 fraction boiling within the range of from about 350' to about 850° F. constitutes a preferred peroxygen compound.and octahydro-anthracenes.. ' pounds suitable as hydrogen transfer catalysts. or both. Based on 100 hydrocarbon compound which contains two oxygen atoms which occupy either ortho or para positions. dimethyl substituted ortho and para dihydroxybenzene and trimethyl and water is contacted and treated with a peroxygen com methylethyl substituted ortho and para dihydroxyben pound.product is separated in phases comprised of from about 6 pounds tov about 12 15 fused or non-fused. ethyl and propyl substituted with or without a preliminary partial evaporation of 30 ortho and para dihydroxybenzene. or compounds. the quinone com boxylic acids which can be added with. Exemplary of the organic car 55 in a given solvent vehicle. pentanoic acid. most often from 6 to about 12 carbon atoms. and ized as containing from 1 to about 4 carbon atoms and one carboxyl group.2 to about 0. and generally the rings are substituted. acetic acid. gen donor compounds. hexahydro. about 210' F. and preferably from about 100° to about tive isomer. or hydrotreating zone. as contrasted with the para-hydroqui conversion reaction is generally conducted at tempera tures ranging from ambient up to the boiling tempera 35 nones and fortunately. of quinones. or reaction product thereof‘. solvent donor vehicle or one wherein the organic carboxylic acid is character precursor. The least catalytically effec-. In conducting the hydroxylation reaction. are formic acid. additional amounts of these materials can be produced. tetrahydronaphthalenes. liquid hydro carbon stream taken from the distillation column em ture of quinone compounds. or an admixture of hydrogen peroxide and a metal salt. In terms 20 of carbon atoms the total molecule generally contains catalysts. are usu 180' F. the aqueous stream dihydroxybenzene. liquid hydrocarbon fraction taken from the coal liquefaction zone has been found to contain a major 5 pounds to be hydroxylated. suitably from about 30' to I present in an essentially 2:1 mole concentration relative to the para-hydroquinones.and decahydro pyrcnes. or the like.e. Preferably both the hydrogen peroxide and organic propionic acid. or injected into the solvent hydrogenation re actor. if desired. e. in view of the relatively high concentration other. Where the quinone is pounds of coal feed. of an admixture of hydro-.032 4 aqueous stream is suitable for recycle to the coal lique The indigenous aqueous fraction separated from the C. hexahy» dro-. these including indane.4 moles. more preferably from about 0. tetrahydro-. and the reaction is gener ally present only in trace amounts within the admixture. are em ployed in the reaction. Exemplary without additional treatment to the coal liquefaction of quinone compounds found in such admixture as reactor. one. the dihydro-. based on the weight of total solvent fed into the coal liquefaction zone. based on the moles of phenolic com . or generated in situ from precursors contained within a suitable solvent donor vehicle. The quinone generally contains from 1 to pounds of water. based on the total weight of the recycled solvent. about 0. ally conducted at ambient pressure. Most while occupying positions ortho or para one to the frequently. The keto or hydroxy groups.. and separated. 4. or compound capable of converting the phenols to dihydroxy benzenes. and octahydro-phenanthrenes.or polycyclic ployed to fractionate the liquid ef?uent from the coal liquefaction reactor is passed into an oil water separator wherein the liquid hydrocarbons and water are strati fied as two distinct phases. suitably a peroxide. Suitably.3 faction zone. nitric acid. generally from about 10 pounds to polycyclic. CIT-C13 acenaph thenes. and most often from pounds of C1-400’ F. nones are present in highest concentration.01 to about 5 percent. alone or in admixture with addi cient to hydroxylize or introduce hydroxyl groups into tional quinone compounds from another source. Formic acid is preferred. the ortho-hydroquinones are ture of the aqueous phase.g. the tetrahydro-. oxygen atom relative to the other. adequate to supply the neces sary hydrogen under coal liquefaction conditions. liquid hydrocarbons. or reacted with pound is added to the solvent fraction in quantity rang the hydrogen peroxide. as well as phenol and alkyl substi tuted phenols. . is the nuclei of the phenolic compounds to convert said phenolic compounds into hydroquinones.1 to ing from about 0. and the like. the C1400‘ F. Preferably also. the meta-dihydroxy benzenes.-400° F. hydrogen chloride. and produces higher hydroxylation of the phenolic compounds on a weight basis than the higher molecular weight organic carbox ylic acids. The quinone catalyst generated in situ in accordance with the present invention is characterized as an admix quantity. These fractions have been found admirably gen peroxide and an organic carboxylic acid. It is a mono. the ditetra. Typically. Hydrogen added to a liquid fraction separated from the liquid products obtained from within the process. however. and the like. phosphoric acid. most often about 50 percent. The aqueous 1 to about 2 rings. Such ferred species. at conditions suitable to convert zene. The ortho-hydroquinones are a pre the phenolic compounds to dihydroxy benzenes. dihydronaphthalene. ‘can be located on the same or different rings.

a liquid product fraction. Subsequent to analysis of the aqueous phase. liquid residence times ranging from about 5 to about 130 minutes.6:1. the sol vent to which the quinone compound has been added. preferably from about 750° F.38 0.~ liquid hydrocarbon portions.07 —- 0. a bottoms fractions boiling above 1000° F.13 10 31 ' a hydrogen donor solvent. and homogeneous catalyst to hydrogenate a hydrogen donor solvent fraction produced from within the coal liquefaction process. or 400°-850° F. Water is separated therefrom. The resultant crystalline material was ana lyzed using mass spectrometry and the relative concen about 1 to about 6 weight percent (MAF coal basis). The 400° F.. All units are in terms of weight unless otherwise speci?ed. and the coal lique?ed. preferably about 1.085. hydro carbons of the 400° F.-400° F. preferably from about 1000 psig to about 1400 psig. depleted hydro gen-donor solvent.g.8:1 to about 2:1. based on weight.. from 400° to 850° F. with pressures ranging from about 300 mass spectrometry was made. fraction. the hy droquinones of the hydroquinone containing aqueous phase were concentrated by drying in a vacuum over psig to about 3000 psig. suitably 8 mesh (Tyler). the results of the analysis being given in the second column of the table. is also recovered and.phenolic compounds. TABLE PHENOLS AND DIHYDROXY BENZENES IN INDIGENOUS WATER FROM COAL LIQUEFACTION REACTORS The product from the coal liquefaction zone 20 con sists of gases and liquids. the admixture of quinone compounds.11 0. if desired. hydrocarbons are drawn off and recovered. A direct analysis of the aqueous phase using In the mixing zone 10. Preferably.— frac the quinone catalyst containing slurry is then intro duced into the solvent hydrogenation reactor 50 or. The separation was accomplished 1. In the best mode of practicing the present invention. schematically illustrated by reference to the FIGURE. and the hydrogenated solvent is recycled as a hydrogen donor solvent to said coal liquefaction zone.boiling range fraction of product coal are admixed in a solvent-to-coal ratio ranging from 40 from the liquid effluent of a Donor Solvent Coal Lique about 0. and a vacuum distillation zone 40B wherein the quinone solids are tion.5 4. In terms of hydrogen donor potential. based on the weight of total solvent introduced into the coal liquefaction zone. pounds. The conditions maintained in hydrogenation zone 50 effec The solvent fraction. These and other features of the present process will be better understood by reference to the following ex emplary data. is introduced into a vacuum distil lation column 40B. other derivatives of partially saturated aromatic com ing char. (d) an oil water separator 40A from which the C1—400° F. prefera aqueous phases with the more dense aqueous phase being bly from about 400° to about 700° F. preferably from about 800° to about 900° F.17 0. preferably from about 800 psig to about 2000 psig. particulate coal of size ranging up to about 5 inch particle size diameter. The liquid mixture is transferred into a separation zone 30 wherein a light fraction boiling below 400° F. Weight Percent In Original Water 0. molecular hydrogen is also added to the liquefaction zone 20 at a rate from [29 inches (of water) vacuum] at l30°-l50° F. to about 900° F. at the time of its introduction into or use within the coal liquefaction zone. — liquid is introduced into an oil-water separator 40A percent.. (c) a distillation and solids separation zone 30 from which is obtained a mixed phase 400° F. 1 concentrated within a slurry faction suitable for recycle by removal of water and (e) a catalytic solvent hydro genation zone 50 wherein the liquid solvent fraction is hydrogenated in the presence of the quinone catalyst admixture. trations thereof is given in the third column of the table. undissolved coal and mineral matter.. for sev eral hours. with molecular hydrogen. The latter is generally used in a gasi?cation process or for coking.000 SCF/B.— product stream withdrawn from frac tionation column 30 is comprised of aqueous and C1-400" F. Temper 2000 psig.. is also introduced into a solvent hydrogenation zone 50 and tively hydrogenate and. liquefaction conditions include a temperature ranging from about 700° to about 950° F. The solvent is one which boils through the density difference between the organic and within the range of about 350° to about 850° F. The preferred hydrogen donor solvent is one produced within the coal liquefaction process. the latter for use as 65 Com onents Phenols C6 c. (b) a coal liquefaction upgrade the hydrogen content of that fraction. which contains generally from about 10 to about 20 percent solids. and preferably from about 1. The coal slurry is decanted. and preferably from about 10 to about 60 min utes. preferably from about 1000 to about 5000 SCF/B. and one which contains suitable quantities of hydrogen donor precur sors. into the coal liquefaction zone 20. e. 25 atures normally range from about 500° to about 1000° F.. is slurried in recycle solvent. is employed as a whereupon the liquids are strati?ed into an upper C. includ Dihndrox benzenes C . a liquid solvent fraction.+ heavy bottoms fraction. Concentration. if desired fed directly or indirectly to the coal liquefaction reactor 20. generally in admixture with . are recovered.. rator from the 400° F. The hydrogen treat rate ranges generally from about 500 to about 10. and an intermediate fraction boiling.06 In Crystals — _ _ C9‘ 0.2:1 to about faction process. the required process steps include (a) a mixing zone 10 within which zone 20 within which the coal slurry is fed. Within the coal liquefaction zone 20. particulate coal is slurried with an internally generated 20 hydrogenated in the presence of a quinone catalyst to liquid solvent donor fraction. and pressures suitably range from about 650 psig to about provided which produce substantial cracking.032 6 . dissolved coal.8 The 400° F.93 0. conditions can be and a l000° F.-— feed from separator 30 are separated from an aqueous component.2 to about 3 per cent of donatable hydrogen. A heavier fraction boiling from about 850° to 1000° F. and the water layer. The solvent and EXAMPLE A water fraction was recovered in an oil-water sepa fed. a majority of which are quinone compounds. as C10 C“ 0. the liquids including a mixture of undepleted hydrogen-donor solvent.16 well. as desired. necessarily contains at least about 0. c.13 0.. In such process.

c. 1. admixture with other compounds.‘ pounds is admixed with an organic carboxylic acid. in a liquefaction zone. the improvement comprising passing said 400‘ F. least 30 weight percent hydrogen donor com 5. Having described the invention what is claimed is: 1. ylic acid is formic acid. hydrogenating said liquid solvent fraction in a hydro 6. said coal feed with 25 3. The process of claim 3 wherein the organic carbox ylic acid is one containing from 1 to about 4 carbon atoms. the presentinvention. — liquid fraction into an oil-water 7. The process of claim 6 wherein the liquid solvent fraction is one boiling within about a 350' to 850' F. 4. hydrocarbon phase. In a process for liquefying a particulate coal feed to 20 duce hydroxyl groups into the nuclei of the phenolic compounds to convert said phenolic compounds into hydroquinones. .7 TABLE-continued PHENOLS AND DIHYDROXY BENZENES IN INDIGENOUS WATER 4. and then recycling said quinone catalyst containing aqueous slurry phase to said solvent hydrogenation zone or to said coal liquefaction zone.18 33. or to said coal liquefaction ‘steps of zone. 2.— liq 40 .90 — ‘Mostly unknown material of MW 136. or to catalyze said reactions.. sufficient to intro. contacting. alone or in .60 0. passing said aque 5 ous slurry phase into a vacuum distillation zone and ‘ whim In Original Water In Crystals removing water from said slurry to concentrate the c.— liquid frac tion and a liquid solvent fraction which contains at said coal liquefaction zone. donor compounds.62 0. separating the product from the liquefaction zone contacted with the aqueous phase to introduce the hy. and the phenolic compounds are converted to quinone catalyst by contacting said aque ous slurry phase with hydrogen peroxide. fraction contains at least 50 weight percent of hydrogen recycling the hydrogenated liquid solvent mixture to into fractions inclusive of a 400' F. F. The process of claim 4 wherein the organic carbox Pounds. range. ous slurry phase obtained by separation of C1-400‘ F. and stratifying said 400' F. Solid Residue H 0 0. a hydrogen donor solvent and a quinone catalyst at temperature and pressure sufficient by hydrocon vert and liquefy the coal. It is apparent that various modi?cations and changes can be made without departing the spirit and scope of tains an admixture of indigenous phenolic compounds and quinone catalyst. c.07 >7l. liquid hydrocarbon 45 55 65 .22 31. The both. ‘ separation zone.. and one carboxylic acid group.032 quinone catalyst.09 quinone catalyst within said phase. process of claim 1 wherein hydrogen peroxide t.10 12.13 0. The process of claim 1 wherein the liquid solvent 35 genation zone.085. 8 phase and an aqueous slurry phase which contains ‘ FROM COAL LIQUEFACI'ION REACTORS separating said aqueous slurry‘ phase from said C1400‘ F. or both.‘ droxyl groups into the nuclei of the phenolic com. to catalyze either or both of these reactions. and .50 1. uid fraction into a C1400‘. The process of claim 1 wherein the separated aque c. and then recycling said stream to said produce useful petroleum-like liquid products by the solvent hydrogenation zone. liquid hydrocarbons therefrom is a slurry which con 15 The slurry of quinone compounds is found highly suitable as a hydrogen transfer catalyst when recycled to the coal liquefaction reactor.